EP0450437B1 - Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use - Google Patents

Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use Download PDF

Info

Publication number
EP0450437B1
EP0450437B1 EP91104620A EP91104620A EP0450437B1 EP 0450437 B1 EP0450437 B1 EP 0450437B1 EP 91104620 A EP91104620 A EP 91104620A EP 91104620 A EP91104620 A EP 91104620A EP 0450437 B1 EP0450437 B1 EP 0450437B1
Authority
EP
European Patent Office
Prior art keywords
weight
polyvinyl alcohol
water
copolymers
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91104620A
Other languages
German (de)
French (fr)
Other versions
EP0450437A3 (en
EP0450437A2 (en
Inventor
Ralf Dr. Brueckmann
Holger Dr. Schoepke
Thomas Dr. Wirth
Juergen Dr. Hartmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0450437A2 publication Critical patent/EP0450437A2/en
Publication of EP0450437A3 publication Critical patent/EP0450437A3/en
Application granted granted Critical
Publication of EP0450437B1 publication Critical patent/EP0450437B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • the invention relates to the copolymers completely or partially neutralized with alkali metal, alkaline earth metal and ammonium salts, a process for the preparation of the copolymers, their use as a means for the temporary surface protection of shaped bodies and flat structures and as a sizing agent for the processing of staple fiber and filament yarns as well as these sizing agents.
  • the invention relates to sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized, sulfo and / or carboxyl group-containing, salt-form water-soluble polyesters of non-aromatic C2-C6 diols and mixtures of aromatic dicarboxylic acids and aromatic Tricarboxylic acids and / or sulfodicarboxylic acids and the use of these sizing agents for the processing of filament yarns.
  • Copolymers prepared by emulsion polymerization in the presence of protective colloids such as polyvinyl alcohol and based on alkyl acrylates and / or methacrylates with minor amounts of other comonomers such as unsaturated carboxylic acids, e.g. Acrylic acid, are known from various publications.
  • the copolymers in the other hand contain a maximum of 7% (US Pat. No. 3,876,596), a maximum of 5% (US Pat. No. 4,670,505) or a maximum of 2% (US Pat. No. 4,265,796) ) very little polyvinyl alcohol as a protective colloid.
  • copolymers described have an undesired sticking of the sized filament threads and experience a large increase in viscosity during neutralization.
  • the recording materials are produced, for example, by coating plastic films with an aqueous coating composition which contains a pigment and a binder as essential constituents.
  • the binder consists of a polymer that is produced by reacting polyvinyl alcohol with methyl methacrylate and acrylic acid.
  • the polymer contains 3 to 20 wt .-% acrylic acid and the ratio of polyvinyl alcohol to methyl methacrylate is 95: 5 to 10: 90.
  • GB-A-1 438 449 discloses the emulsion polymerization of acrylates, methacrylates and butadiene in the presence of hydrolyzed vinyl acetate / alkali metal olefin sulfonate copolymers.
  • the acrylates and methacrylates can also be copolymerized in a mixture with acrylic acid or methacrylic acid.
  • the aqueous polymer dispersions obtainable in this way can be used, for example, as an adhesive, coating agent, extraordinarilyl or paper auxiliary.
  • the object of the present invention is to provide new sizing agents.
  • Sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized sulfo and / or carboxyl groups containing salt-water-soluble polyesters from non-aromatic C2-C6 diols and mixtures of aromatic dicarboxylic acids and Wegn tricarboxylic acids and / or -sulfodicarboxylic acids found.
  • the copolymers to be used according to the invention are from 50 to 95 wt .-%, preferably 70 to 80 wt .-% of a C1-C8 alkyl acrylate and / or methacrylate as component A and 5 to 20 wt .-% of an unsaturated carboxylic acid as a component B in the presence of 2 to 60 parts by weight, preferably 10 to 40 parts by weight of polyvinyl alcohol, based on 100 parts by weight of A and B.
  • copolymers to be used according to the invention can also be built up from up to 20% by weight of further water-soluble comonomers as component C and from up to 10% by weight of other comonomers as component D.
  • component A are C1-C8 alkyl acrylates and / or methacrylates.
  • Particularly preferred components A are methyl and n-butyl acylate and / or methacrylate.
  • Ethyl, n-propyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl acrylate or methacrylate are preferred.
  • n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl and n-octyl acrylate or methacrylate are mentioned.
  • unsaturated carboxylic acids come into consideration primarily acrylic acid and methacrylic acid.
  • Crotonic acid, maleic acid, fumaric acid, itaconic acid and the anhydrides of unsaturated carboxylic acids are also suitable.
  • Additional water-soluble comonomers as component C are, above all, acrylamide, methacrylamide, allyl alcohol and very particularly acrylonitrile and sodium vinyl sulfonate.
  • component D preferably vinyl aromatics such as styrene, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and the esters of unsaturated dicarboxylic acids such as the di-n-butyl ester of maleic acid.
  • vinyl aromatics such as styrene, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and the esters of unsaturated dicarboxylic acids such as the di-n-butyl ester of maleic acid.
  • the polyvinyl alcohols used as component E preferably have a degree of polymerization of 200 to 2000 and a degree of hydrolysis of 75 to 99 mol%. The remaining 1 to 25 mol% are accounted for by acetate or propionate groups of the polyvinyl acetate or propionate preferably used for the production of the polyvinyl alcohol.
  • polyvinyl alcohols with a degree of polymerization of 300 to 2000 (corresponding to a standard viscosity of 3 to 25 mPa ⁇ s) and a degree of saponification of 86 to 90 mol% are preferred.
  • copolymers to be used according to the invention are prepared by free-radical solution polymerization, preferably by free-radical emulsion polymerization in aqueous solution.
  • the usual peroxo or azo compounds can be used as initiators for the radical polymerization reaction Reducing agents, advantageously in amounts of 0.5 to 2.0 wt .-%, based on the weight of the monomers.
  • Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane To name cumene hydroperoxide and 4,4'-azobisisobutyronitrile.
  • Preferred reducing agents are hydrazine, sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, ammonium sulfite and ammonium hydrogen sulfite, which are used in amounts of 0.005 to 2.0% by weight.
  • Preferred emulsifiers are anionic emulsifiers such as lauryl sulfate, p-n-nonylphenol, p-n-decylphenol, sodium stearate, potassium oleate and especially C15 paraffin sulfonate.
  • Suitable nonionic emulsifiers are preferably the oxyethylation products of lauryl alcohol, oleyl alcohol, stearyl alcohol, oleic acid and stearic amide, oleyl amide and stearic and oleic acid with a degree of oxyethylation of 3 to 20.
  • cationic emulsifiers such as ammonium, phosphonium and sulfonium compounds are also suitable a long aliphatic hydrocarbon chain as a hydrophobic part of the molecule.
  • the emulsifiers important for emulsion polymerization are used in amounts of 0.1 to 2.0% by weight.
  • Regulators can be added to control the molecular mass. It is particularly important to use a regulator with larger quantities of polyvinyl alcohol, since without a regulator it is possible to form highly viscous, non-flowable solutions that are less suitable as sizing agents.
  • Preferred regulators are carbon tetrachloride, carbon tetrabromide, benzyl bromide, trichlorobromomethane and butyl mercaptan, which are generally used in amounts of 0.1 to 5% by weight.
  • tert. -Dodecyl mercaptan as a regulator in amounts of 0.2 to 1.0% by weight in combination with 1.0 to 1.5% by weight of a peroxo compound as an initiator.
  • the polymerization is carried out at 20 to 95 ° C., preferably at 65 to 90 ° C.
  • reaction is expediently carried out at normal pressure, but it is also possible to work under reduced or slightly increased pressure, that is to say in the range from 0.5 to 5 bar.
  • the reaction times are usually 1 to 5, usually 2 to 3 hours.
  • the emulsion feed process is generally carried out in such a way that an aqueous solution of some of the initiators, emulsifiers and regulators is heated to the reaction temperature and the monomers are fed in the same or changing proportions, preferably continuously. It is also possible to add a portion of the monomers, preferably 4 to 20% by weight, to start the polymerization and to start adding the majority of the monomer mixture after about 10 to 30 minutes.
  • the polyvinyl alcohol can be added at the same time or with a time lag with the monomers; amounts of up to 10% by weight are preferably introduced in the aqueous solution.
  • the remaining portions of the initiators, emulsifiers and regulators are added continuously or intermittently.
  • the polymerization is expediently continued, with the addition of further amounts of initiator, for a period of about 1 hour in order to lower residual monomer contents.
  • the copolymers are preferably converted into their sodium, calcium, magnesium, ammonium or C1-C4-alkylammonium salts at temperatures between 50 and 85 ° C.
  • the proportion of the salts is at least 50%.
  • the aqueous latex is preferably treated with aqueous ammonia.
  • Staple fiber sizing is preferably obtained by adding sodium hydroxide solution, sodium carbonate or sodium hydrogen carbonate to the aqueous latex.
  • solutions thus obtainable can be used directly or together with other components as sizing agents for polyester, cellulose acetate, polyamide, viscose, cotton, cotton / polyester, viscose / polyester and for polyester / wool fibers.
  • polyesters defined as component c) are known or can be obtained by known methods (Ullmann, Vol. 23, p. 17 (1983).
  • non-aromatic C2-C6 diols such as diethylene glycol or 1,4-hydroxymethylcyclohexane and a mixture of an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid and an aromatic tricarboxylic acid and / or sulfodicarboxylic acid such as trimellitic acid and / or sulfoisophthalic acid.
  • Polyesters with molecular weights of 150,000 to 250,000 and an acid number of 40 to 60 mg of potassium hydroxide per free polymer are preferably used.
  • Thickeners, pigments, crosslinking agents, fillers, reinforcing agents, filming aids and antioxidants are also suitable.
  • the polymer mixtures according to the invention are preferably produced by combining acrylate and / or methacrylate copolymers, polyvinyl alcohol, polyester and optionally conventional additives as a 15 to 25% by weight solution.
  • the copolymers and polymer mixtures according to the invention preferably have K values of 25 to 120, particularly 30 to 50.
  • the desired K value in each case can be set in a manner known per se by choosing the polymerization conditions, primarily the duration of the polymerization and the initiator concentration.
  • the K values are measured according to Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 (1932) at 25 ° C in 0.5% by weight tetrahydrofuran solution and represent a measure of the molecular weight.
  • the dispersions or solutions of the copolymers and polymer mixtures according to the invention have solids contents of preferably 20 to 50% by weight, the partially neutralized or neutralized dispersions or solutions preferably have solids contents of 18 to 25% by weight.
  • copolymers according to the invention are mainly used as sizing agents for processing staple fiber and filament yarns
  • the polymer mixtures according to the invention are preferably used as sizing agents for processing microfiber yarns, multifilament yarns and textured or smooth filament yarns.
  • They can also be used to temporarily protect the surface of flat or spatial structures, such as drawings, maps, prints, photos or images.
  • copolymers according to the invention are notable for their good sizing effect, while at the same time having a high film hardness and hence a low tendency to stick together the sized filament threads. Furthermore they show high adhesive strength values as well as mixture stability and low viscosity. A particular advantage of these copolymers is that they can be easily washed out before further processing of the yarns.
  • the viscosities of the copolymers given in the examples were measured in a Brookfield viscometer at 100 rpm and a temperature of 20 ° C. in aqueous solution at the concentrations given in each case.
  • copolymers prepared according to methods a) and b) were obtained in the form of aqueous dispersions by the emulsion polymerization process. After addition of a base, the copolymer dispersed in water dissolved in each case with the formation of clear aqueous copolymer solutions.
  • the mixture was then polymerized for 1 hour, cooled to 55 ° C and neutralized to pH 7.4 with 15% aqueous sodium hydroxide solution.
  • the solution obtained had a polymer content of 20.6% by weight and a viscosity of 2450 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 600.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 10 g polyvinyl alcohol 25.7 g feed 2
  • the solution obtained had a polymer content of 25.1% by weight and a viscosity of 166 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 842 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 20 g polyvinyl alcohol 25.5 g feed 2
  • the solution obtained had a polymer content of 21.7% by weight and a viscosity of 298 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 832.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 25.7 g feed 2
  • the solution obtained had a polymer content of 20.3% by weight and a viscosity of 1660 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 400.3 g of water 0.2 g of a C-15 paraffin sulfonate 0.8 g sodium vinyl sulfonate 25.4 g feed 2.
  • the solution obtained had a polymer content of 20.5% by weight and a viscosity of 1640 mPa ⁇ s at 20 ° C.
  • the film properties and the pilling values and the pseudo warp thread break values were determined as the application properties of the copolymers according to the invention and as a measure of the sizing effect.
  • yarns of polyester / cotton in a weight ratio of 65:35 were sized at room temperature with 15% liquors of the copolymers on a laboratory sizing machine (DE-PS 2 714 897). The sized yarns were then held at 68% relative humidity and 20 ° C for 24 hours.
  • Table 1 shows the results of tests A and B on the film properties and the sizing effect.
  • the copolymers 1 to 5 according to the invention are completely tough, elastic and homogeneous and have high pilling and pseudo warp thread break values with regard to the sizing effect.
  • This copolymer was prepared analogously to Example 1 with the following in the template and feeds 1 and 2. However, the neutralization was carried out with 25% aqueous ammonia. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 25.7 g feed 2
  • the solution obtained had a polymer content of 20.7% by weight and a viscosity of 1800 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium sulfonate 25.7 g feed 2
  • the solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa ⁇ s at 20 ° C.
  • the thread closure and the tendency to blocking were determined as the application properties of the copolymers according to the invention.
  • the thread closure is a measure of the quality of a size in relation to the protection and stabilization of the thread.
  • the Shirley filament counter is used to determine the thread closure by cutting the filament thread before and after finishing and determining the number of free, unglued individual filaments from the pulses counted during cutting.
  • the raw yarn has a manra value of 100, i.e. 100% of the individual filaments are unglued.
  • the lower the manra value the more individual filaments are glued to the interface and the better the thread closure and the thread adhesion and thus the achievable weaving effect.
  • test yarns made of polyester filament, smooth, dtex 50 f 18 with 6% size layer were used, which were both measured directly with the Shirley filament counter (Manra value M0 in Table 2), as well as 200 stress cycles were exposed before the measurement on the Reutlingen web tester (Manra value M200 in Table 2).
  • Blocking is an undesired sticking of the cut filament threads.
  • sized filament bundles with a size of 6 to 7% by weight were placed between two glass plates of 5 x 5 cm in size under pressure of an attached weight of 1 kg at 65% relative humidity and 21 ° C. for the duration of Stored for 3 days.
  • Table 2 shows the results of tests A and B and the proportion of polyvinyl alcohol in the copolymers of Examples 6 and 7.
  • copolymers 6 and 7 according to the invention show good thread closure without a tendency to block.
  • Table 2 Application properties of the copolymers according to Examples 6 and 7 Sizing agents PVA [%] Thread closure Blocking M0 M200 according to example 6 19th 20th 29 No according to example 7 10th 15 33 No
  • This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 734.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 10.0 g polyvinyl alcohol 107.8 g feed 1
  • the solution obtained had a polymer content of 24.2% by weight and a viscosity of 110 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 20 g polyvinyl alcohol 138.1 g feed 2
  • the solution obtained had a polymer content of 20.1% by weight and a viscosity of 128 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 161.7 g feed 1
  • the solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 174.7 g feed 1
  • the solution obtained had a polymer content of 20.4% by weight and a viscosity of 1620 mPa ⁇ s at 20 ° C.
  • This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 190 g feed 1
  • the solution obtained had a polymer content of 20.6% by weight and a viscosity of 1400 mPa ⁇ s at 20 ° C.
  • This polyester with -COOH groups was obtained by condensation of 1 mole of diethylene glycol 0.54 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane) 1.12 moles of isophthalic acid 0.2 mole of terephthalic acid 0.23 mole trimellitic anhydride manufactured.
  • the neutralization was carried out with ammonia / triethanolamine in a ratio of 6: 4.
  • This polyester with -SO3H groups was by condensation of 0.86 mole of diethylene glycol 0.2 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane) 0.23 mole of isophthalic acid 0.70 mole of terephthalic acid 0.13 mole of sulfoisophthalic acid manufactured.
  • the neutralization was carried out with sodium salt up to pH 5.6.
  • the thread closure values were determined as a performance characteristic of the polymer mixtures according to the invention.
  • Table 3 shows the results of this test and the chemical composition in polymer mixtures 8 to 11.
  • the corresponding individual components are given as examples C to G.
  • the pure polyvinyl alcohol is compared.
  • the polymer mixtures 8 to 11 according to the invention show better thread closure or adhesive strength values and better abrasion resistance than the associated individual components.
  • Table 3 Adhesive strength of the polymer mixtures 8 to 11 according to the invention in comparison to corresponding individual components example Chemical composition Thread closure M 0 M 200 C.
  • Table 4 shows the results of the determination of the stability and viscosity of the polymer mixtures 8, 9 and 10 according to the invention.
  • the comparative mixtures were prepared from one of the individual components A or B, polyvinyl alcohol and water and from the individual component F.
  • the polymer mixtures 8 to 10 according to the invention are stable to the mixtures with the individual components A and B.
  • Table 4 Stability and viscosity of the polymer mixtures 8 to 10 according to the invention in comparison with mixtures of individual components with a low polyvinyl alcohol content Methacrylate example used Acrylate / copolymer PVA content [%] Stability of the mixture Viscosity of the 15% liquor A 2nd Separation after 4 days 70/50 B 4th Separation after 7 days 80/50 C. 10th no separation 120/110 D 19th no separation 235/275 E 25th no separation 215/225

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Paper (AREA)

Description

Die vorliegende Erfindung betrifft Copolymerisate auf der Basis von C₁-C₈-Alkylacrylaten und/oder -methacrylaten, erhältlich durch radikalische Emulsions- oder Lösungspolymerisation von

  • A) 50 bis 95 Gew.-% eines C₁-C₈-Alkylacrylates und/oder -methacrylates,
  • B) 5 bis 20 Gew.-% einer ungesättigten Carbonsäure und/oder eines ungesättigten Carbonsäureanhydrids,
  • C) 0 bis 20 Gew.-% weiterer wasserlöslicher Comonomerer und
  • D) 0 bis 10 Gew.-% sonstiger Comonomerer in Gegenwart von
  • E) 2 bis 60 Gew.-Teilen Polyvinylalkohol pro 100 Gew.-Teile des Monomerengemisches aus A) bis D).
The present invention relates to copolymers based on C₁-C₈ alkyl acrylates and / or methacrylates, obtainable by radical emulsion or solution polymerization of
  • A) 50 to 95% by weight of a C₁-C₈ alkyl acrylate and / or methacrylate,
  • B) 5 to 20% by weight of an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride,
  • C) 0 to 20% by weight of further water-soluble comonomers and
  • D) 0 to 10% by weight of other comonomers in the presence of
  • E) 2 to 60 parts by weight of polyvinyl alcohol per 100 parts by weight of the monomer mixture from A) to D).

Außerdem betrifft die Erfindung die mit Alkalimetall-, Erdalkalimetall- und Ammoniumsalzen vollständig oder partiell neutralisierten Copolymerisate, ein Verfahren zur Herstellung der Copolymerisate, deren Verwendung als Mittel zum vorübergehenden Oberflächenschutz von Form-Körpern und Flächengebilden und als Schlichtemittel für die Verarbeitung von Stapelfaser- und Filamentgarnen sowie diese Schlichtemittel.In addition, the invention relates to the copolymers completely or partially neutralized with alkali metal, alkaline earth metal and ammonium salts, a process for the preparation of the copolymers, their use as a means for the temporary surface protection of shaped bodies and flat structures and as a sizing agent for the processing of staple fiber and filament yarns as well as these sizing agents.

Weiterhin betrifft die Erfindung Schlichtemittel aus den beschriebenen Acrylat- und/oder Methacrylatcopolymeren, Polyvinylalkohol, üblichen Zusatzstoffen und vollständig oder partiell neutralisierte, Sulfo- und/oder Carboxylgruppen enthaltenden, in Salzform wasserlöslichen Polyestern aus nichtaromatischen C₂-C₆-Diolen und Gemischen aromatischer Dicarbonsäuren und aromatischer Tricarbonsäuren und/oder -sulfodicarbonsäuren sowie die Verwendung dieser Schlichtemittel für die Verarbeitung von Filamentgarnen.Furthermore, the invention relates to sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized, sulfo and / or carboxyl group-containing, salt-form water-soluble polyesters of non-aromatic C₂-C₆ diols and mixtures of aromatic dicarboxylic acids and aromatic Tricarboxylic acids and / or sulfodicarboxylic acids and the use of these sizing agents for the processing of filament yarns.

Durch Emulsionspolymerisation in Gegenwart von Schutzkolloiden wie Polyvinylalkohol hergestellte Copolymerisate auf der Basis von Alkylacrylaten und/oder -methacrylaten mit untergeordneten Mengen weiterer Comonomerer wie ungesättigten Carbonsäuren, z.B. Acrylsäure, sind aus diversen Veröffentlichungen bekannt.Copolymers prepared by emulsion polymerization in the presence of protective colloids such as polyvinyl alcohol and based on alkyl acrylates and / or methacrylates with minor amounts of other comonomers such as unsaturated carboxylic acids, e.g. Acrylic acid, are known from various publications.

In diesen Copolymerisaten, die sich vornehmlich als Bindemittel für Dispersionsfarben und als Klebstoffe eignen, ist der Anteil der ungesättigten Carbonsäure mit maximal 5 % (GB 1 278 813) oder mit 1 % (DE-A 3 111 602) sehr gering.In these copolymers, which are primarily suitable as binders for emulsion paints and as adhesives, the proportion of unsaturated carboxylic acid with a maximum of 5% (GB 1 278 813) or with 1% (DE-A 3 111 602) very low.

Ist der Anteil der ungesättigten Carbonsäure höher, so enthalten die Copolymerisate andererseits mit maximal 7 % (US-A 3 876 596), mit maximal 5 % (US-A 4 670 505) oder mit maximal 2 % (US-A 4 265 796) nur sehr wenig Polyvinylalkohol als Schutzkolloid.If the proportion of unsaturated carboxylic acid is higher, the copolymers on the other hand contain a maximum of 7% (US Pat. No. 3,876,596), a maximum of 5% (US Pat. No. 4,670,505) or a maximum of 2% (US Pat. No. 4,265,796) ) very little polyvinyl alcohol as a protective colloid.

Diese Copolymerisate sind für manche Zwecke aber nur bedingt geeignet.However, these copolymers are only of limited use for some purposes.

Aus Ullmann, Bd. 23, S. 16 (1983) sind Copolymerisate auf der Basis von Acrylat- und/oder Methacrylatcopolymeren bekannt, die als Schlichtemittel empfohlen werden.Ullmann, vol. 23, p. 16 (1983) discloses copolymers based on acrylate and / or methacrylate copolymers, which are recommended as sizing agents.

Die beschriebenen Copolymerisate weisen jedoch ein unerwünschtes Verkleben der geschlichteten Filamentfäden auf und erfahren bei der Neutralisation einen großen Viskositätszuwachs.However, the copolymers described have an undesired sticking of the sized filament threads and experience a large increase in viscosity during neutralization.

Aus der JP-A-62/288076 sind Aufzeichnungsmaterialien für Tintenstrahldrucker bekannt. Die Aufzeichnungsmaterialien werden beispielsweise durch Beschichten von Folien aus Kunststoff mit einer wäßrigen Beschichtungsmasse hergestellt, die als wesentliche Bestandteile ein Pigment und einen Binder enthält. Der Binder besteht aus einem Polymer, das durch Reaktion von Polyvinyl-alkohol mit Methylmethacrylat und Acrylsäure hergestellt wird. Das Polymer enthält 3 bis 20 Gew.-% Acrylsäure und das Verhältnis von Polyvinylalkohol zu Methylmethacrylat beträgt 95 : 5 bis 10 : 90.From JP-A-62/288076 recording materials for ink jet printers are known. The recording materials are produced, for example, by coating plastic films with an aqueous coating composition which contains a pigment and a binder as essential constituents. The binder consists of a polymer that is produced by reacting polyvinyl alcohol with methyl methacrylate and acrylic acid. The polymer contains 3 to 20 wt .-% acrylic acid and the ratio of polyvinyl alcohol to methyl methacrylate is 95: 5 to 10: 90.

Aus der GB-A-1 438 449 ist die Emulsionspolymerisation von Acrylaten, Methacrylaten und Butadien in Gegenwart von hydrolysierten Vinylacetat/Alkalimetall-Olefinsulfonat-Copolymerisaten bekannt. Die Acrylate und Methacrylate können auch in Mischung mit Acrylsäure oder Methacrylsäure copolymerisiert werden. Die so erhältlichen wäßrigen Polymerdispersionen können beispielsweise als Klebstoff, Beschichtungsmittel, extilbehandlungsmittel oder Papierhilfsmittel verwendet werden.GB-A-1 438 449 discloses the emulsion polymerization of acrylates, methacrylates and butadiene in the presence of hydrolyzed vinyl acetate / alkali metal olefin sulfonate copolymers. The acrylates and methacrylates can also be copolymerized in a mixture with acrylic acid or methacrylic acid. The aqueous polymer dispersions obtainable in this way can be used, for example, as an adhesive, coating agent, exquisite treatment agent or paper auxiliary.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, neue Schlichtemittel zur Verfügung zu stellen.The object of the present invention is to provide new sizing agents.

Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von Copolymerisaten, die erhältlich sind durch radikalische Emulsions- oder Lösungspolymerisation von

  • A) 50 bis 95 Gew.-% eines C₁-C₈-Alkylacrylates und/oder -methacrylates,
  • B) 5 bis 20 Gew.-% einer ungesättigten Carbonsäure und/oder eines ungesättigten Carbonsäureanhydrids,
  • C) 0 bis 20 Gew.-% weiterer wasserlöslicher Comonomerer und
  • D) 0 bis 10 Gew.-% sonstiger Comonomerer
    in Gegenwart von
  • E) 2 bis 60 Gew.-Teilen Polyvinylalkohol pro 100 Gew.-Teile des Monomerengemisches aus A) bis D)
und die vollständig oder partiell als Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze vorliegen, als Schlichtemittel für Stapelfaser- und Filamentgarne.The object is achieved according to the invention with the use of copolymers which can be obtained by radical emulsion or solution polymerization of
  • A) 50 to 95% by weight of a C₁-C₈ alkyl acrylate and / or methacrylate,
  • B) 5 to 20% by weight of an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride,
  • C) 0 to 20% by weight of further water-soluble comonomers and
  • D) 0 to 10% by weight of other comonomers
    in the presence of
  • E) 2 to 60 parts by weight of polyvinyl alcohol per 100 parts by weight of the monomer mixture from A) to D)
and which are present completely or partially as alkali metal, alkaline earth metal or ammonium salts, as sizing agents for staple fiber and filament yarns.

Weiterhin wurden Schlichtemittel aus den beschriebenen Acrylat-und/oder Methacrylatcopolymeren, Polyvinylalkohol, üblichen Zusatzstoffen und vollständig oder partiell neutralisierten Sulfo- und/oder Carboxylgruppen enthaltenden, in Salzform wasserlöslichen Polyestern aus nichtaromatischen C₂-C₆-Diolen und Gemischen aromatischer Dicarbonsäuren und aroatischer Tricarbonsäuren und/oder -Sulfodicarbonsäuren gefunden.Sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized sulfo and / or carboxyl groups containing salt-water-soluble polyesters from non-aromatic C₂-C₆ diols and mixtures of aromatic dicarboxylic acids and Croatian tricarboxylic acids and / or -sulfodicarboxylic acids found.

Die erfindungsgemäß zu verwendenden Copolymerisate werden aus 50 bis 95 Gew.-%, vorzugsweise 70 bis 80 Gew.-% eines C₁-C₈-Alkylacrylates und/oder -methacrylates als Komponente A und 5 bis 20 Gew.-% einer ungesättigten Carbonsäure als Komponente B in Gegenwart von 2 bis 60 Gew.-Teilen, vorzugsweise 10 bis 40 Gew.-Teilen Polyvinylalkohol, bezogen auf 100 Gew.-Teile A und B, hergestellt.The copolymers to be used according to the invention are from 50 to 95 wt .-%, preferably 70 to 80 wt .-% of a C₁-C₈ alkyl acrylate and / or methacrylate as component A and 5 to 20 wt .-% of an unsaturated carboxylic acid as a component B in the presence of 2 to 60 parts by weight, preferably 10 to 40 parts by weight of polyvinyl alcohol, based on 100 parts by weight of A and B.

Außerdem können die erfindungsgemäß zu verwendenden Copolymerisate aus bis zu 20 Gew.-% weiteren wasserlöslichen Comonomeren als Komponente C und aus bis zu 10 Gew.-% sonstigen Comonomeren als Komponente D mitaufgebaut sein.In addition, the copolymers to be used according to the invention can also be built up from up to 20% by weight of further water-soluble comonomers as component C and from up to 10% by weight of other comonomers as component D.

Als Komponente A eignen sich C₁-C₈-Alkylacrylate und/oder -methacrylate.As component A are C₁-C₈ alkyl acrylates and / or methacrylates.

Besonders bevorzugte Komponenten A sind Methyl- und n-Butylacylat und/oder -methacrylat.Particularly preferred components A are methyl and n-butyl acylate and / or methacrylate.

Bevorzugt sind Ethyl-, n-Propyl-, iso-Propyl-, iso-Butyl-, sec.-Butyl-, tert.-Butylacrylat bzw. -methacrylat.Ethyl, n-propyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl acrylate or methacrylate are preferred.

Daneben sind n-Pentyl-, n-Hexyl-, 2-Ethylhexyl-, n-Heptyl- und n-Octylacrylat bzw. -methacrylat zu nennen.In addition, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl and n-octyl acrylate or methacrylate are mentioned.

Als Komponente B kommen ungesättigte Carbonsäuren in Betracht vornehmlich die Acrylsäure und Methacrylsäure.As component B, unsaturated carboxylic acids come into consideration primarily acrylic acid and methacrylic acid.

Weiterhin eignen sich die Crotonsäure, Maleinsäure, Fumarsäure, Itaconsäure und die Anhydride der ungesättigten Carbonsäuren.Crotonic acid, maleic acid, fumaric acid, itaconic acid and the anhydrides of unsaturated carboxylic acids are also suitable.

Zusätzliche wasserlösliche Comonomere als Komponente C sind vor allem Acrylamid, Methacrylamid, Allylalkohol und ganz besonders Acrylnitril und Natriumvinylsulfonat.Additional water-soluble comonomers as component C are, above all, acrylamide, methacrylamide, allyl alcohol and very particularly acrylonitrile and sodium vinyl sulfonate.

Für die Komponente D kommen sonstige Comonomere in Betracht, bevorzugt Vinylaromaten wie Styrol, Vinylacetat, Vinylpropionat, N-Vinylpyrrolidon und die Ester von ungesättigten Dicarbonsäuren wie der Di-n-butylester der Maleinsäure.Other comonomers are suitable for component D, preferably vinyl aromatics such as styrene, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and the esters of unsaturated dicarboxylic acids such as the di-n-butyl ester of maleic acid.

Die als Komponente E verwendeten Polyvinylalkohole haben vorzugsweise einen Polymerisationsgrad von 200 bis 2000 und einen Hydrolysegrad von 75 bis 99 mol-%. Die restlichen 1 bis 25 mol-% entfallen auf Acetat- oder Propionatgruppen des für die Herstellung des Polyvinylalkohols vorzugsweise verwendeten Polyvinylacetats bzw. -propionats.The polyvinyl alcohols used as component E preferably have a degree of polymerization of 200 to 2000 and a degree of hydrolysis of 75 to 99 mol%. The remaining 1 to 25 mol% are accounted for by acetate or propionate groups of the polyvinyl acetate or propionate preferably used for the production of the polyvinyl alcohol.

Zur Herstellung einer Filamentschlichte sind Polyvinylalkohole mit einem Polymerisationsgrad von 300 bis 2000 (entsprechend einer Standardviskosität von 3 bis 25 mPa·s) und einem Verseifungsgrad von 86 bis 90 mol-% bevorzugt.For the production of a filament size, polyvinyl alcohols with a degree of polymerization of 300 to 2000 (corresponding to a standard viscosity of 3 to 25 mPa · s) and a degree of saponification of 86 to 90 mol% are preferred.

Die erfindungsgemäß zu verwendenden Copolymerisate werden durch radikalische Lösungspolymerisation, vorzugsweise durch radikalische Emulsionspolymerisation in wäßriger Lösung hergestellt.The copolymers to be used according to the invention are prepared by free-radical solution polymerization, preferably by free-radical emulsion polymerization in aqueous solution.

Als Initiatoren für die radikalisch ablaufende Polymerisationsreaktion können die üblichen Peroxo- oder Azoverbindungen, auch in Kombination mit Reduktionsmitteln, zweckmäßigerweise in Mengen von 0,5 bis 2,0 Gew.-%, bezogen auf das Gewicht der Monomeren, eingesetzt werden.The usual peroxo or azo compounds, also in combination with, can be used as initiators for the radical polymerization reaction Reducing agents, advantageously in amounts of 0.5 to 2.0 wt .-%, based on the weight of the monomers.

Als bevorzugte Initiatoren sind Dibenzoylperoxid, tert.-Butylperpivalat, tert.-Butylper-2-ethylhexanoat, Di-tert.-butylperoxid, tert.-Butylhydroperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)hexan, Cumolhydroperoxid und 4,4'-Azobisisobutyronitril zu nennen.Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane To name cumene hydroperoxide and 4,4'-azobisisobutyronitrile.

Bevorzugte Reduktionsmittel sind Hydrazin, Natriumsulfit, Natriumhydrogensulfit, Kaliumsulfit, Kaliumhydrogensulfit, Ammoniumsulfit und Ammoniumhydrogensulfit, die in Mengen von 0,005 bis 2,0 Gew.-% eingesetzt werden.Preferred reducing agents are hydrazine, sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, ammonium sulfite and ammonium hydrogen sulfite, which are used in amounts of 0.005 to 2.0% by weight.

Bevorzugte Emulgatoren sind anionische Emulgatoren wie Laurylsulfat, p-n-Nonylphenol, p-n-Decylphenol, Natriumstearat, Kaliumoleat und vor allem C₁₅-Paraffinsulfonat. Als nichtionische Emulgatoren eignen sich vorzugsweise die Oxethylierungsprodukte des Laurylalkohols, Oleylalkohols, Stearylalkohols, Ölsäure- und Stearinamids, Oleylamids sowie der Stearin- und Ölsäure mit einem Oxethylierungsgrad von 3 bis 20. Ferner kommen auch kationische Emulgatoren wie Ammonium-, Phosphonium- und Sulfoniumverbindungen mit mindestens einer langen aliphatischen Kohlenwasserstoffkette als hydrophoben Molekülteil in Betracht.Preferred emulsifiers are anionic emulsifiers such as lauryl sulfate, p-n-nonylphenol, p-n-decylphenol, sodium stearate, potassium oleate and especially C₁₅ paraffin sulfonate. Suitable nonionic emulsifiers are preferably the oxyethylation products of lauryl alcohol, oleyl alcohol, stearyl alcohol, oleic acid and stearic amide, oleyl amide and stearic and oleic acid with a degree of oxyethylation of 3 to 20. Furthermore, cationic emulsifiers such as ammonium, phosphonium and sulfonium compounds are also suitable a long aliphatic hydrocarbon chain as a hydrophobic part of the molecule.

Die für eine Emulsionspolymerisation wichtigen Emulgatoren werden in Mengen von 0,1 bis 2,0 Gew.-% eingesetzt.The emulsifiers important for emulsion polymerization are used in amounts of 0.1 to 2.0% by weight.

Zur Steuerung der Molekularmasse können Regler zugesetzt werden. Besonders wichtig ist die Mitverwendung eines Reglers bei größeren Mengen Polyvinylalkohol, da es ohne einen Regler zur Bildung hochviskoser, nicht fließfähiger Lösungen kommen kann, die als Schlichtemittel weniger in Betracht kommen.Regulators can be added to control the molecular mass. It is particularly important to use a regulator with larger quantities of polyvinyl alcohol, since without a regulator it is possible to form highly viscous, non-flowable solutions that are less suitable as sizing agents.

Bevorzugte Regler sind Tetrachlorkohlenstoff, Tetrabromkohlenstoff, Benzylbromid, Trichlorbrommethan und Butylmercaptan, die im allgemeinen in Mengen von 0,1 bis 5 Gew.-% eingesetzt werden.Preferred regulators are carbon tetrachloride, carbon tetrabromide, benzyl bromide, trichlorobromomethane and butyl mercaptan, which are generally used in amounts of 0.1 to 5% by weight.

Besonders gute Ergebnisse erzielt man mit tert. -Dodecylmercaptan als Regler in Mengen von 0,2 bis 1,0 Gew.-% in Kombination mit 1,0 bis 1,5 Gew.-% einer Peroxoverbindung als Initiator.Particularly good results are achieved with tert. -Dodecyl mercaptan as a regulator in amounts of 0.2 to 1.0% by weight in combination with 1.0 to 1.5% by weight of a peroxo compound as an initiator.

Im allgemeinen führt man die Polymerisation bei 20 bis 95°C vorzugsweise bei 65 bis 90°C durch.In general, the polymerization is carried out at 20 to 95 ° C., preferably at 65 to 90 ° C.

Zweckmäßigerweise wird die Umsetzung bei Normaldruck vorgenommen, jedoch kann man auch bei vermindertem oder leicht erhöhtem Druck arbeiten, also etwa im Bereich von 0,5 bis 5 bar.The reaction is expediently carried out at normal pressure, but it is also possible to work under reduced or slightly increased pressure, that is to say in the range from 0.5 to 5 bar.

Die Reaktionszeiten betragen normalerweise 1 bis 5, meistens 2 bis 3 Stunden.The reaction times are usually 1 to 5, usually 2 to 3 hours.

Verfahrenstechnisch geht man nach dem Emulsions-Zulaufverfahren in der Regel so vor, daß man eine wäßrige Lösung aus einem Teil der Initiatoren, Emulgatoren und Regler auf die Reaktionstemperatur erhitzt und die Monomeren in gleichen oder wechselnden Anteilen, vorzugsweise kontinuierlich zuführt. Es ist auch möglich, einen Teil der Monomeren bevorzugt 4 bis 20 Gew.-% mitvorzulegen, die Polymerisation zu starten und erst nach etwa 10 bis 30 Minuten mit dem Zulauf der Hauptmenge des Monomerengemisches zu beginnen.In terms of process engineering, the emulsion feed process is generally carried out in such a way that an aqueous solution of some of the initiators, emulsifiers and regulators is heated to the reaction temperature and the monomers are fed in the same or changing proportions, preferably continuously. It is also possible to add a portion of the monomers, preferably 4 to 20% by weight, to start the polymerization and to start adding the majority of the monomer mixture after about 10 to 30 minutes.

Der Polyvinylalkohol kann zeitgleich oder zeitversetzt mit den Monomeren zugegeben werden, bevorzugt werden Mengen bis zu 10 Gew.-% in der wäßrigen Lösung vorgelegt. Die restlichen Anteile der Initiatoren, Emulgatoren und Regler werden kontinuierlich oder intermittierend zugesetzt.The polyvinyl alcohol can be added at the same time or with a time lag with the monomers; amounts of up to 10% by weight are preferably introduced in the aqueous solution. The remaining portions of the initiators, emulsifiers and regulators are added continuously or intermittently.

Nach beendetem Zulauf setzt man die Polymerisation zweckmäßigerweise unter Zusatz weiterer Initiatormengen noch etwa für eine Zeit von 1 Stunde fort, um Restmonomerengehalte abzusenken.After the feed has ended, the polymerization is expediently continued, with the addition of further amounts of initiator, for a period of about 1 hour in order to lower residual monomer contents.

Zur Herstellung der Schlichtemittel überführt man die Copolymerisate bevorzugt bei Temperaturen zwischen 50 und 85°C in ihre Natrium-, Calcium-, Magnesium-, Ammonium- oder die C₁-C₄-Alkylammoniumsalze. Im allgemeinen beträgt der Anteil der Salze mindestens 50 %.To prepare the sizing agents, the copolymers are preferably converted into their sodium, calcium, magnesium, ammonium or C₁-C₄-alkylammonium salts at temperatures between 50 and 85 ° C. In general, the proportion of the salts is at least 50%.

Sollen die Schlichtemittel zur Ausrüstung von Filamentgarnen dienen, so behandelt man den wäßrigen Latex bevorzugt mit wäßrigem Ammoniak.If the sizing agents are used to finish filament yarns, the aqueous latex is preferably treated with aqueous ammonia.

Stapelfaserschlichten erhält man vorzugsweise durch Zugabe von Natronlauge, Natriumcarbonat oder Natriumhydrogencarbonat zum wäßrigen Latex.Staple fiber sizing is preferably obtained by adding sodium hydroxide solution, sodium carbonate or sodium hydrogen carbonate to the aqueous latex.

Man kann die so erhältlichen Lösungen unmittelbar oder zusammen mit weiteren Komponenten als Schlichtemittel für Polyester-, Celluloseacetat-, Polyamid-, Viskose-, Baumwolle-, Baumwolle/Polyester-, Viskose/Polyesterund für Polyester/Wolle-Fasern verwenden.The solutions thus obtainable can be used directly or together with other components as sizing agents for polyester, cellulose acetate, polyamide, viscose, cotton, cotton / polyester, viscose / polyester and for polyester / wool fibers.

Besonders gut geeignet sind Schlichtemittel aus

  • a) 20 bis 60 Gew.-%, vorzugsweise 40 bis 60 Gew.-% eines definitionsgemäßen, vollständig oder partiell neutralisierten Acrylat- und/oder Methacrylatcopolymers,
  • b) 10 bis 40 Gew.-%, vorzugsweise 10 bis 25 Gew.-% Polyvinylalkohol mit einem bevorzugten Hydrolysegrad von 85 bis 90 mol-%,
  • c) 20 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-% eines vollständig oder partiell neutralisierten, Sulfo- und/oder Carboxylgruppen enthaltenden, in Salzform wasserlöslichen Polyesters aus einem nichtaromatischen C₂-C₆-Diol und einem Gemisch einer aromatischen Dicarbonsäure und einer aromatischen Tricarbonsäure und/oder -Sulfodiccarbonsäure und
  • d) 0 bis 10 Gew.-% üblicher Zusatzstoffe.
Sizing agents made from are particularly suitable
  • a) 20 to 60% by weight, preferably 40 to 60% by weight, of a fully or partially neutralized acrylate and / or methacrylate copolymer as defined,
  • b) 10 to 40% by weight, preferably 10 to 25% by weight, of polyvinyl alcohol with a preferred degree of hydrolysis of 85 to 90 mol%,
  • c) 20 to 60 wt .-%, preferably 20 to 50 wt .-% of a completely or partially neutralized, sulfo and / or carboxyl-containing, salt-form water-soluble polyester from a non-aromatic C₂-C₆ diol and a mixture of an aromatic dicarboxylic acid and an aromatic tricarboxylic acid and / or sulfodiccarboxylic acid and
  • d) 0 to 10% by weight of conventional additives.

Die als Komponente c) definierten Polyester sind bekannt oder nach bekannten Methoden erhältlich (Ullmann, Bd. 23, S. 17 (1983).The polyesters defined as component c) are known or can be obtained by known methods (Ullmann, Vol. 23, p. 17 (1983).

Man gewinnt sie durch Kondensation von nichtaromatischen C₂-C₆-Diolen wie Diethylenglykol oder 1,4-Hydroxymethylcyclohexan und einem Gemisch einer aromatischen Dicarbonsäure wie iso-Phthalsäure oder Terephthalsäure und einer aromatischen Tricarbonsäure und/oder -Sulfodicarbonsäure wie Trimellithsäure und/oder Sulfoisophthalsäure.It is obtained by condensing non-aromatic C₂-C₆ diols such as diethylene glycol or 1,4-hydroxymethylcyclohexane and a mixture of an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid and an aromatic tricarboxylic acid and / or sulfodicarboxylic acid such as trimellitic acid and / or sulfoisophthalic acid.

Bevorzugt werden Polyester mit Molekulargewichten von 150 000 bis 250 000 und einer Säurezahl von 40 bis 60 mg Kaliumhydroxid pro Gratis Polymer eingesetzt.Polyesters with molecular weights of 150,000 to 250,000 and an acid number of 40 to 60 mg of potassium hydroxide per free polymer are preferably used.

Als übliche Zusatzstoffe d sind zu nennen:

  • Viskositätsregulatoren wie Perborate, Wasserstoffperoxid und Harnstoff;
  • Schlichtefette wie sulfatierte Fette und Öle und primäre Fettalkoholsulfate;
  • Netzmittel wie sulfierte Öle, Fettalkoholsulfate und aromatische Sulfonate;
  • Entschäumer wie Amide oder Ester von Fettsäuren und Silicone und
  • Konservierungsmittel wie Kupfersulfat, Aluminiumalaun, Borsäure, Formaldehyd und Benzoesäure.
The usual additives d are:
  • Viscosity regulators such as perborates, hydrogen peroxide and urea;
  • Size greases such as sulfated fats and oils and primary fatty alcohol sulfates;
  • Wetting agents such as sulfated oils, fatty alcohol sulfates and aromatic sulfonates;
  • Defoamers such as amides or esters of fatty acids and silicones and
  • Preservatives such as copper sulfate, aluminum alum, boric acid, formaldehyde and benzoic acid.

Weiterhin kommen Verdickungsmittel, Pigmente, Vernetzer, Füllstoffe, Verstärkungsmittel, Verfilmungshilfsmittel und Antioxidantien in Betracht.Thickeners, pigments, crosslinking agents, fillers, reinforcing agents, filming aids and antioxidants are also suitable.

Die erfindungsgemäßen Polymermischungen werden vorzugsweise durch Zusammengeben von Acrylat- und/oder Methacrylatcopolymeren, Polyvinylalkohol, Polyester und gegebenenfalls üblichen Zusatzstoffen als 15 bis 25 gew.-%ige Lösung hergestellt.The polymer mixtures according to the invention are preferably produced by combining acrylate and / or methacrylate copolymers, polyvinyl alcohol, polyester and optionally conventional additives as a 15 to 25% by weight solution.

Die Copolymerisate und Polymermischungen gemäß der Erfindung weisen bevorzugt K-Werte von 25 bis 120, besonders 30 bis 50, auf. Der jeweils gewünschte K-Wert läßt sich in an sich bekannter Weise durch Wahl der Polymerisationsbedingungen, in erster Linie der Polymerisat onsdauer und der Initiatorkonzentration, einstellen.The copolymers and polymer mixtures according to the invention preferably have K values of 25 to 120, particularly 30 to 50. The desired K value in each case can be set in a manner known per se by choosing the polymerization conditions, primarily the duration of the polymerization and the initiator concentration.

Die K-Werte werden nach Fikentscher, Cellulose-Chemie, Bd. 13, S. 58 bis 64 (1932) bei 25°C in 0,5 gew.-%iger Tetrahydrofuranlösung gemessen und stellen ein Maß für das Molgewicht dar.The K values are measured according to Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 (1932) at 25 ° C in 0.5% by weight tetrahydrofuran solution and represent a measure of the molecular weight.

Die Dispersionen oder Lösungen der erfindungsgemäßen Copolymerisate und Polymermischungen weisen Feststoffgehalte von vorzugsweise 20 bis 50 Gew.-% auf, die teilneutralisierten oder neutralisierten Dispersionen oder Lösungen haben vorzugsweise Feststoffgehalte von 18 bis 25 Gew.-%.The dispersions or solutions of the copolymers and polymer mixtures according to the invention have solids contents of preferably 20 to 50% by weight, the partially neutralized or neutralized dispersions or solutions preferably have solids contents of 18 to 25% by weight.

Die erfindungsgemäßen Copolymerisate finden hauptsächlich a s Schlichtemittel für die Verarbeitung von Stapelfaser- und Filamentgarnen Verwendung, die erfindungsgemäßen Polymermischungen dienen bevorzugt als Schlichtemittel für die Verarbeitung von Mikrofasergarnen, Multifilamentgarnen und texturierten oder glatten Filamentgarnen.The copolymers according to the invention are mainly used as sizing agents for processing staple fiber and filament yarns, the polymer mixtures according to the invention are preferably used as sizing agents for processing microfiber yarns, multifilament yarns and textured or smooth filament yarns.

Außerdem können sie zum vorübergehenden Oberflächenschutz von flächigen oder räumlichen Gebilden, beispielsweise Zeichnungen, Karte, Drucken, Fotos oder Bildern benutzt werden.They can also be used to temporarily protect the surface of flat or spatial structures, such as drawings, maps, prints, photos or images.

Des weiteren eignen sie sich als Papierverfestiger, Druckverdicker, Textilausrüstungsmittel und als Klebemittel.They are also suitable as paper strengthening agents, pressure thickeners, textile finishing agents and as adhesives.

Die Copolymerisate gemäß der Erfindung zeichnen sich durch ihre gute Schlichtewirkung bei gleichzeitig hoher Filmhärte und damit geringer Neigung zum Verkleben der geschlichteten Filamentfäden aus. Des weiteren zeigen sie hohe Klebkraftwerte sowie Mischungsstabilität und geringe Viskosität. Ein besonderer Vorteil dieser Copolymerisate ist die leichte Auswaschbarkeit vor der Weiterverarbeitung der Garne.The copolymers according to the invention are notable for their good sizing effect, while at the same time having a high film hardness and hence a low tendency to stick together the sized filament threads. Furthermore they show high adhesive strength values as well as mixture stability and low viscosity. A particular advantage of these copolymers is that they can be easily washed out before further processing of the yarns.

Die in den Beispielen angegebenen Viskositäten der Copolymerisate wurden in einem Brookfield-Viskosimeter bei 100 UpM und einer Temperatur von 20°C in wäßriger Lösung bei den jeweils angegebenen Konzentrationen gemessen.The viscosities of the copolymers given in the examples were measured in a Brookfield viscometer at 100 rpm and a temperature of 20 ° C. in aqueous solution at the concentrations given in each case.

BeispieleExamples

Die gemäß den Methoden a) und b) hergestellten Copolymerisate wurden nach dem Verfahren der Emulsionspolymerisation in Form wäßriger Dispersionen erhalten. Nach Zugabe einer Base löste sich das in Wasser dispergierte Copolymerisat jeweils unter Bildung klarer wäßriger Copolymerisatlösungen.The copolymers prepared according to methods a) and b) were obtained in the form of aqueous dispersions by the emulsion polymerization process. After addition of a base, the copolymer dispersed in water dissolved in each case with the formation of clear aqueous copolymer solutions.

a) Herstellung von Copolymerisaten, die vornehmlich als Stapelfaserschlichtemittel geeignet sinda) Production of copolymers which are primarily suitable as staple fiber sizing agents

In den folgenden Beispielen 1 bis 5 wurde ein Polyvinylalkool (hergestellt durch Hydrolyse von Polyvinylacetat) mit einem Hydrolysegrad von 88 mol-% und einem Polymerisationsgrad von 400 (entsprechen einer Standardviskosität - gemessen bei 20°C an 4%igen wäßrigen Lösungen - von 4 mPa·s) verwendet.In the following Examples 1 to 5, a polyvinyl alcohol (produced by hydrolysis of polyvinyl acetate) with a degree of hydrolysis of 88 mol% and a degree of polymerization of 400 (corresponding to a standard viscosity - measured at 20 ° C. in 4% aqueous solutions - of 4 mPa · S) used.

Beispiel 1example 1

Eine Lösung aus
842,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
20 g Polyvinylalkohol und
25,7 g Zulauf 2
wurde nach dem Erwärmen auf 80°C im Laufe von 2 bis 2,5 Stunden bei 85°C kontinuierlich mit den Zuläufen 1 und 2 versetzt.A solution
842.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
20 g polyvinyl alcohol and
25.7 g feed 2
After heating to 80 ° C., feeds 1 and 2 were continuously added over the course of 2 to 2.5 hours at 85 ° C.

Zulauf 1Inlet 1

846,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril846.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Danach wurde 1 Stunde nachpolymerisiert, auf 55°C abgekühlt und mit 15%iger wäßriger Natronlauge bis pH 7,4 neutralisiert.The mixture was then polymerized for 1 hour, cooled to 55 ° C and neutralized to pH 7.4 with 15% aqueous sodium hydroxide solution.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,6 Gew.-% und eine Viskosität von 2450 mPa·s bei 20°C.The solution obtained had a polymer content of 20.6% by weight and a viscosity of 2450 mPa · s at 20 ° C.

Beispiel 2Example 2

Dieses Copolymerisat wurde analog Beispiel 1 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
600,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
10 g Polyvinylalkohol
25,7 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
600.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
10 g polyvinyl alcohol
25.7 g feed 2

Zulauf 1Inlet 1

572,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril572.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 25,1 Gew.-% und bei 20°C eine Viskosität von 166 mPa·s.The solution obtained had a polymer content of 25.1% by weight and a viscosity of 166 mPa · s at 20 ° C.

Beispiel 3Example 3

Dieses Copolymerisat wurde analog Beispiel 1 mit der nachfolgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
842 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
20 g Polyvinylalkohol
25,5 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
842 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
20 g polyvinyl alcohol
25.5 g feed 2

Zulauf 1Inlet 1

839,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril839.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 21,7 Gew.-% und bei 20°C eine Viskosität von 298 mPa·s.The solution obtained had a polymer content of 21.7% by weight and a viscosity of 298 mPa · s at 20 ° C.

Beispiel 4Example 4

Dieses Copolymerisat wurde analog Beispiel 1 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
832,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
25,7 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
832.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
25.7 g feed 2

Zulauf 1Inlet 1

896,9 g Wasser
333,3 g 30%ige wäßrige Lösung von Polyvinylalkohol
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril896.9 g water
333.3 g of 30% aqueous solution of polyvinyl alcohol
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,3 Gew.-% und bei 20°C eine Viskosität von 1660 mPa·s.The solution obtained had a polymer content of 20.3% by weight and a viscosity of 1660 mPa · s at 20 ° C.

Beispiel 5Example 5

Dieses Copolymerisat wurde analog Beispiel 1 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
400,3 g Wasser
0,2 g eines C-15-Paraffinsulfonats
0,8 g Natriumvinylsulfonat
25,4 g Zulauf 2.This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
400.3 g of water
0.2 g of a C-15 paraffin sulfonate
0.8 g sodium vinyl sulfonate
25.4 g feed 2.

Zulauf 1Inlet 1

661,7 g Wasser
500 g 30%ige wäßrige Lösung von Polyvinylalkohol
1,16 g eines C-15-Paraffinsulfonats
0,4 g Natriumvinylsulfonat
1,2 g tert.-Dodecylmercaptan
42 g Methacrylsäure
168 g n-Butylacrylat
69 g Methylmethacrylat
21 g Acrylnitril661.7 g water
500 g of 30% aqueous solution of polyvinyl alcohol
1.16 g of a C-15 paraffin sulfonate
0.4 g sodium vinyl sulfonate
1.2 g of tert-dodecyl mercaptan
42 g methacrylic acid
168 g of n-butyl acrylate
69 g methyl methacrylate
21 g acrylonitrile

Zulauf 1Inlet 1

250 g Wasser
4,2 g Natriumpersulfat.250 g water
4.2 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,5 Gew.-% und bei 20°C eine Viskosität von 1640 mPa·s.The solution obtained had a polymer content of 20.5% by weight and a viscosity of 1640 mPa · s at 20 ° C.

Anwendungstechnische EigenschaftenApplication properties

Als anwendungstechnische Eigenschaften der erfindungsgemäßen Copolymerisate wurden die Filmeigenschaften und als Maß für die Schlichtewirkung die Pilling-Werte sowie die Pseudokettfadenbruch-Werte ermittelt.The film properties and the pilling values and the pseudo warp thread break values were determined as the application properties of the copolymers according to the invention and as a measure of the sizing effect.

A) Bestimmung der FilmeigenschaftenA) Determination of film properties

Zur Ermittlung der Filmeigenschaften werden mechanische Eigenschaften wie Elastizität sowie Homogenität und Zähigkeit der Filme geprüft.To determine the film properties, mechanical properties such as elasticity and homogeneity and toughness of the films are tested.

Zur Bestimmung der Filmeigenschafen wurden aus den Polymerlösungen gemäß den Beispielen 1 bis 5 2 mm dicke Folien hergestellt. Anschließend wurden diese Filme für die Dauer von 3 Stunden bei 80°C getrocknet und danach 24 Stunden bei 65 % bzw. 80 % relativer Feuchtigkeit und 20°C gehalten.To determine the properties of the film, 2 to 2 mm thick films were produced from the polymer solutions according to Examples 1 to 5. These films were then dried at 80 ° C. for 3 hours and then kept at 65% or 80% relative humidity and 20 ° C. for 24 hours.

B) Bestimmung der Schlichtewirkung durch ErmittlungB) Determination of the sizing effect by determination

  • a) der Pilling-Werte und
  • b) der Pseudo-Kettfadenbruch-Werte

Die Prüfung der Schlichtewirkung erfolgt auf dem Reutlinger Webtester, der die Belastung der Kettgarne beim Webvorgang simuliert, indem geschlichtete Garne unter einer bestimmten Spannung mittels Metallstiften wiederholt mechanisch beansprucht werden (J. Trauter u. R. Vialon, Textil Praxis International 1985, 1201). Die Anzahl dieser Beanspruchungen, bei der eine bestimmte Schädigung des Garns festzustellen ist, stellt ein Maß für die Qualität des Schlichtemittels dar.
  • a) the pilling values and
  • b) the pseudo warp thread break values

The sizing effect is tested on the Reutlingen weaving tester, which simulates the load on the warp yarns during the weaving process by repeatedly mechanically stressing sized yarns under a certain tension using metal pins (J. Trauter and R. Vialon, Textil Praxis International 1985, 1201). The number of these stresses, at which a certain damage to the yarn can be determined, represents a measure of the quality of the sizing agent.

Als Kriterium für die Schlichtewirkung dienenServe as a criterion for the sizing effect

  • a) die Pilling-Werte unda) the pilling values and
  • b) die Pseudo-Kettfadenbruch-Werte.b) the pseudo warp thread break values.
  • a) Der Pilling-Wert ist derjenige Wert, bei dem die Bildung eines Knötchens an einem bestimmten Garn zu beobachten ist.a) The pilling value is the value at which the formation of a nodule on a particular yarn can be observed.
  • b) Der Pseudo-Kettfadenbruch-Wert ist derjenige Wert, bei dem ein bestimmtes Garn erschlafft.b) The pseudo warp thread break value is the value at which a particular yarn slackens.

Hohe Pilling- und Pseudo-Kettfadenbruch-Werte bedeuten eine gute Schlichtewirkung.High pilling and pseudo warp thread break values mean a good sizing effect.

Zur Bestimmung der Schlichtewirkung wurden Garne aus Polyester/Baumwolle im Gewichtsverhältnis 65 : 35 bei Raumtemperatur mit 15%igen Flotten der Copolymeren auf einer Laborschlichtmaschine (DE-PS 2 714 897) geschlichtet. Anschließend wurden die geschlichteten Garne für die Dauer von 24 Stunden bei 68 % relativer Feuchtigkeit und 20°C gehalter.To determine the sizing effect, yarns of polyester / cotton in a weight ratio of 65:35 were sized at room temperature with 15% liquors of the copolymers on a laboratory sizing machine (DE-PS 2 714 897). The sized yarns were then held at 68% relative humidity and 20 ° C for 24 hours.

Die Tabelle 1 zeigt die Ergebnisse der Prüfungen A und B auf die Filmeigenschaften und die Schlichtewirkung. Die erfindungsgemäßen Copolymerisate 1 bis 5 sind vollkommen zäh, elastisch und homogen und zeigen bezüglich der Schlichtewirkung hohe Pilling- und Pseudo-Kettfadenbruch-Werte. Tabelle 1 Anwendungstechnische Eigenschaften der Copolymerisate gemäß den Beispielen 1 bis 5 Schlichtemittel Filmeigenschaften Schlichtewirkung Pilling Pseudo-Kettfadenbruch gemäß Beispiel 1 zäh, elastisch, homogen 4307 4728 gemäß Beispiel 2 zäh, elastisch, homogen 2593 4028 gemäß Beispiel 3 zäh, elastisch, homogen 2442 3944 gemäß Beispiel 4 zäh, elastisch, homogen 2055 3250 gemäß Beispiel 5 zäh, elastisch, homogen 2010 3041 Zum Vergleich: zäh, elastisch, homogen 683 2336 Handelsübliche Schlichte* * Copolymerisat aus 65 % Acrylsäure und 35 % Acrylnitril, Ammoniumsalz Table 1 shows the results of tests A and B on the film properties and the sizing effect. The copolymers 1 to 5 according to the invention are completely tough, elastic and homogeneous and have high pilling and pseudo warp thread break values with regard to the sizing effect. Table 1 Application properties of the copolymers according to Examples 1 to 5 Sizing agents Film properties Sizing effect Pilling Pseudo warp thread break according to example 1 tough, elastic, homogeneous 4307 4728 according to example 2 tough, elastic, homogeneous 2593 4028 according to example 3 tough, elastic, homogeneous 2442 3944 according to example 4 tough, elastic, homogeneous 2055 3250 according to example 5 tough, elastic, homogeneous 2010 3041 For comparison: tough, elastic, homogeneous 683 2336 Commercial size * * Copolymer of 65% acrylic acid and 35% acrylonitrile, ammonium salt

b) Herstellung von Copolymerisaten, die vornehmlich als Filamentschlichtemittel geeignet sindb) Production of copolymers which are primarily suitable as filament size agents

In den folgenden Beispielen 6 und 7 wurde ein Polyvinylalkolol (hergestellt durch Hydrolyse von Polyvinylacetat) mit einem Hydrolysegrad von 88 mol-% und einem Polymerisationsgrad von 500 (entsprechend einer Standardviskosität - gemessen bei 20°C an 4%igen wäßrigen Lösungen - von 5 mPa·s) verwendet.In Examples 6 and 7 below, a polyvinyl alcohol (produced by hydrolysis of polyvinyl acetate) with a degree of hydrolysis of 88 mol% and a degree of polymerization of 500 (corresponding to a standard viscosity - measured at 20 ° C. in 4% strength aqueous solutions - of 5 mPa · S) used.

Beispiel 6Example 6

Dieses Copolymerisat wurde analog Beispiel 1 mit der folgend in Vorlage sowie den Zuläufen 1 und 2 hergestellt. Die Neutralisation erfolgte jedoch mit 25%igem wäßrigem Ammoniak.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
25,7 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following in the template and feeds 1 and 2. However, the neutralization was carried out with 25% aqueous ammonia.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
25.7 g feed 2

Zulauf 1Inlet 1

738,9 g Wasser
475 g 20%ige wäßrige Polyvinylalkohol-Lösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
70 g Methacrylsäure
250 g n-Butylacrylat
25 g n-Butylmethacrdylat
120 g Methylmethacrylat
15 g Styrol
20 g Acrylnitril738.9 g water
475 g 20% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
70 g methacrylic acid
250 g n-butyl acrylate
25 g n-butyl methacrylate
120 g methyl methacrylate
15 g styrene
20 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,7 Gew.-% und bei 20°C eine Viskosität von 1800 mPa·s.The solution obtained had a polymer content of 20.7% by weight and a viscosity of 1800 mPa · s at 20 ° C.

Beispiel 7Example 7

Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumsulfonat
25,7 g Zulauf 2This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium sulfonate
25.7 g feed 2

Zulauf 1Inlet 1

945,9 g Wasser
166,6 g 30%ige wäßrige Polyvinylalkohol-Lösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril945.9 g water
166.6 g 30% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 19,6 Gew.-% und bei 20°C eine Viskosität von 152 mPa·s.The solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa · s at 20 ° C.

Anwendungstechnische EigenschaftenApplication properties

Als anwendungstechnische Eigenschaften der erfindungsgemäßer Copolymerisate wurden der Fadenschluß und die Blocking-Neigung ermittelt.The thread closure and the tendency to blocking were determined as the application properties of the copolymers according to the invention.

A) Bestimmung des FadenschlussesA) Determination of the thread closure

Der Fadenschluß ist ein Maß für die Güte einer Schlichte in bezug auf den Schutz und die Stabilisierung des Fadens. Die Bestimmung des Fadenschlusses erfolgt mit dem Shirley-Filamentcounter, indem der Filamentfaden vor und nach dem Schlichten durchgeschnitten wird und aus den beim Schneiden gezählten Impulsen die Anzahl der freien, unverklebten Einzelfilamente ermittelt wird.The thread closure is a measure of the quality of a size in relation to the protection and stabilization of the thread. The Shirley filament counter is used to determine the thread closure by cutting the filament thread before and after finishing and determining the number of free, unglued individual filaments from the pulses counted during cutting.

Das Rohgarn besitzt einen Manra-Wert von 100, d.h. 100 % der Einzelfilamente sind unverklebt. Je niedriger der Manra-Wert, desto mehr Einzelfilamente sind an der Schnittstelle verklebt und desto besser sind der Fadenschluß sowie die Fadenhaftung und damit der erzielbare Webnutzeffekt.The raw yarn has a manra value of 100, i.e. 100% of the individual filaments are unglued. The lower the manra value, the more individual filaments are glued to the interface and the better the thread closure and the thread adhesion and thus the achievable weaving effect.

Zur Bestimmung des Fadenschlusses wurden Testgarne aus Polyester-Filament, glatt, dtex 50 f 18 mit 6 % Schlichteauflage verwendet, die sowohl direkt mit dem Shirley-Filamentcounter gemessen wurden (Manra-Wert M0 in Tabelle 2), als auch vor der Messung auf dem Reutlinger Webtester 200 Beanspruchungszyklen ausgesetzt waren (Manra-Wert M200 in Tabelle 2).To determine the thread closure, test yarns made of polyester filament, smooth, dtex 50 f 18 with 6% size layer were used, which were both measured directly with the Shirley filament counter (Manra value M0 in Table 2), as well as 200 stress cycles were exposed before the measurement on the Reutlingen web tester (Manra value M200 in Table 2).

Gute Klebkraftwerte und guter Fadenschluß sind bei M200-Werten unter 50 und bei einer möglichst geringen Differenz zwischen den MO- und M200-Wer-ten gegeben.Good adhesive strength values and good thread closure are given with M200 values below 50 and with the smallest possible difference between the MO and M200 values.

B) Bestimmung der Blocking-NeigungB) Determination of the blocking tendency

Als Blocking wird ein unerwünschtes Verkleben der geschlichieten Filamentfäden bezeichnet.Blocking is an undesired sticking of the cut filament threads.

Zur Bestimmung der Blocking-Neigung wurden geschlichtete Filamentbündel mit einer Schlichteauflage von 6 bis 7 Gew.-% zwischen zwei Glasplatten von 5 x 5 cm Größe unter Druck eines aufgesetzten Gewichtes von 1 kg bei 65 % relativer Feuchtigkeit und 21°C für die Dauer von 3 Tagen gelagert.To determine the blocking tendency, sized filament bundles with a size of 6 to 7% by weight were placed between two glass plates of 5 x 5 cm in size under pressure of an attached weight of 1 kg at 65% relative humidity and 21 ° C. for the duration of Stored for 3 days.

Die Tabelle 2 zeigt die Ergebnisse der Prüfungen A und B sowie den Anteil an Polyvinylalkohol in den Copolymerisaten der Beispiele 6 und 7.Table 2 shows the results of tests A and B and the proportion of polyvinyl alcohol in the copolymers of Examples 6 and 7.

Die erfindungsgemäßen Copolymerisate 6 und 7 zeigen einen guten Fadenschluß ohne Blocking-Neigung. Tabelle 2 Anwendungstechnische Eigenschaften der Copolymerisate gemäß den Beispielen 6 und 7 Schlichtemittel PVA [%] Fadenschluß Blocking M0 M200 gemäß Beispiel 6 19 20 29 nein gemäß Beispiel 7 10 15 33 nein The copolymers 6 and 7 according to the invention show good thread closure without a tendency to block. Table 2 Application properties of the copolymers according to Examples 6 and 7 Sizing agents PVA [%] Thread closure Blocking M0 M200 according to example 6 19th 20th 29 No according to example 7 10th 15 33 No

c) Herstellung von Polymermischungen, die vornehmlich als Filamentschlichtemittel geeignet sindc) Production of polymer mixtures which are primarily suitable as filament size agents Einzelkomponente ASingle component A

Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
734,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
10,0 g Polyvinylalkohol
107,8 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
734.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
10.0 g polyvinyl alcohol
107.8 g feed 1

Zulauf 1Inlet 1

572,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2,0 g tert.-Dodecylmercaptan
70,0 g Methacrylsäure
280,0 g n-Butylacrylat
115,0 g Methylmethacrylat
35,0 g Acrylnitril572.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2.0 g of tert-dodecyl mercaptan
70.0 g methacrylic acid
280.0 g of n-butyl acrylate
115.0 g methyl methacrylate
35.0 g acrylonitrile

Zulauf 2Inlet 2

250 g Wasser
7,0 g Natriumpersulfat.250 g water
7.0 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 24,2 Gew.-% und bei 20°C eine Viskosität vom 110 mPa·s.The solution obtained had a polymer content of 24.2% by weight and a viscosity of 110 mPa · s at 20 ° C.

Einzelkomponente BSingle component B

Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
20 g Polyvinylalkohol
138,1 g Zulauf 2This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
20 g polyvinyl alcohol
138.1 g feed 2

Zulauf 1Inlet 1

875,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure875.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,1 Gew.-% und bei 20°C eine Viskosität von 128 mPa·s.The solution obtained had a polymer content of 20.1% by weight and a viscosity of 128 mPa · s at 20 ° C.

Einzelkomponente CSingle component C

Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
161,7 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
161.7 g feed 1

Zulauf 1Inlet 1

945,9 g Wasser
166,6 g 30%ige wäßrige Polyvinylalkohollösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure945.9 g water
166.6 g of 30% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 19,6 Gew.-% und bei 20°C eine Viskosität von 152 mPa·s.The solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa · s at 20 ° C.

Einzelkomponente DSingle component D

Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
174,7 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
174.7 g feed 1

Zulauf 1Inlet 1

768,9 g Wasser
475 g 20%ige wäßrige Polyvinylalkohollösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure768.9 g water
475 g 20% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid

Zulauf 2Inlet 2

250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,4 Gew.-% und bei 20°C eine Viskosität von 1620 mPa·s.The solution obtained had a polymer content of 20.4% by weight and a viscosity of 1620 mPa · s at 20 ° C.

Einzelkomponente ESingle component E

Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
190 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
190 g feed 1

Zulauf 1Inlet 1

770,9 g Wasser
625 g 20%ige wäßrige Polyvinylalkohollösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure770.9 g water
625 g of 20% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid

Zulauf 2Inlet 2

768 g Wasser
7 g Natriumpersulfat.768 g water
7 g sodium persulfate.

Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,6 Gew.-% und bei 20°C eine Viskosität von 1400 mPa·s.The solution obtained had a polymer content of 20.6% by weight and a viscosity of 1400 mPa · s at 20 ° C.

Einzelkomponente FSingle component F

Dieser Polyester mit -COOH-Gruppen wurde durch Kondensation von
1 Mol Diethylenglykol
0,54 Mol Cyclohexandimethanol (1,4-Hydroxymethylcyclohexan)
1,12 Mol iso-Phthalsäure
0,2 Mol Terephthalsäure
0,23 Mol Trimellithsäureanhydrid
hergestellt. Die Neutralisation erfolgte mit Ammoniak/Triethanolamin im Verhältnis 6 : 4.This polyester with -COOH groups was obtained by condensation of
1 mole of diethylene glycol
0.54 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane)
1.12 moles of isophthalic acid
0.2 mole of terephthalic acid
0.23 mole trimellitic anhydride
manufactured. The neutralization was carried out with ammonia / triethanolamine in a ratio of 6: 4.

Einzelkomponente GSingle component G

Dieser Polyester mit -SO₃H-Gruppen wurde durch Kondensation von
0,86 Mol Diethylenglykol
0,2 Mol Cyclohexandimethanol (1,4-Hydroxymethylcyclohexan)
0,23 Mol iso-Phthalsäure
0,70 Mol Terephthalsäure
0,13 Mol Sulfoisophthalsäure
hergestellt. Die Neutralisation erfolgte mit Natriumsalz bis zu pH 5,6.This polyester with -SO₃H groups was by condensation of
0.86 mole of diethylene glycol
0.2 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane)
0.23 mole of isophthalic acid
0.70 mole of terephthalic acid
0.13 mole of sulfoisophthalic acid
manufactured. The neutralization was carried out with sodium salt up to pH 5.6.

Beispiele 8 bis 11Examples 8 to 11

Die erfindungsgemäßen Polymermischungen 8 bis 11 wurden in der Kälte in einem solchen Verhältnis aus

  • Schlichtelösung aus einer der Einzelkomponenten C bis E
  • Polyvinylalkohol und Wasser und
  • Polyesterschlichtelösung aus einer der Einzelkomponenten F oder G
hergestellt, daß eine ca. 20 gew.-%ige Mischung mit einem Polymeranteil aus
  • 21 % Polyvinylalkohol als Summe aus dem Polyvinylalkoho anteil der Einzelkomponente und separat zugesetztem Polyvinylalkohol
  • 50 % Acrylat/Methacrylat-Copolymer und
  • 29 % Polyester
entstand.The polymer mixtures 8 to 11 according to the invention were made in the cold in such a ratio
  • Sizing solution from one of the individual components C to E
  • Polyvinyl alcohol and water and
  • Polyester sizing solution from one of the individual components F or G
made that an approximately 20 wt .-% mixture with a polymer content
  • 21% polyvinyl alcohol as the sum of the polyvinyl alcohol portion of the individual component and separately added polyvinyl alcohol
  • 50% acrylate / methacrylate copolymer and
  • 29% polyester
originated.

Als anwendungstechnische Eigenschaft der erfindungsgemäßen Polymermischungen wurden die Fadenschlußwerte ermittelt.The thread closure values were determined as a performance characteristic of the polymer mixtures according to the invention.

Die Tabelle 3 zeigt die Ergebnisse dieser Prüfung sowie die chemische Zusammensetzung in den Polymermischungen 8 bis 11. Zum Vergleich sind als Beispiele C bis G die entsprechenden Einzelkomponenten angegeben. Außerdem ist der reine Polyvinylalkohol gegenübergestellt.Table 3 shows the results of this test and the chemical composition in polymer mixtures 8 to 11. For comparison, the corresponding individual components are given as examples C to G. In addition, the pure polyvinyl alcohol is compared.

Die erfindungsgemäßen Polymermischungen 8 bis 11 zeigen bessere Fadenschluß- bzw. Klebkraftwerte sowie bessere Abriebfestigkeit als die zugehörigen Einzelkomponenten. Tabelle 3 Klebkraft der erfindungsgemäßen Polymermischungen 8 bis 11 im Vergleich zu entsprechenden Einzelkomponenten Beispiel Chemische Zusammensetzung Fadenschluß M 0 M 200 C Acrylat/Methacrylat, 10 Gew.-% PVA 15 33 D Acrylat/Methacrylat, 19 Gew.-% PVA 12 16 E Acrylat/Methacrylat, 25 Gew.-% PVA 13 36 F Polyester mit Carboxylgruppen 18 41 G Polyester mit Sulfonsäuregruppen 15 18 8 Polymermischung mit C und F 13 21 9 Polymermischung mit D und F 10 13 10 Polymermischung mit E und F 10 22 11 Polymermischung mit D und G 15 25 PVA (88/5) Polyvinylalkohol (erhalten aus Polyvinylacetat) zu 88 % verseift, Viskosität (4 % in Wasser, 20°C) 5 mPa·s 32 >90 The polymer mixtures 8 to 11 according to the invention show better thread closure or adhesive strength values and better abrasion resistance than the associated individual components. Table 3 Adhesive strength of the polymer mixtures 8 to 11 according to the invention in comparison to corresponding individual components example Chemical composition Thread closure M 0 M 200 C. Acrylate / methacrylate, 10 wt% PVA 15 33 D Acrylate / methacrylate, 19 wt% PVA 12th 16 E Acrylate / methacrylate, 25 wt% PVA 13 36 F Polyester with carboxyl groups 18th 41 G Polyester with sulfonic acid groups 15 18th 8th Polymer blend with C and F 13 21 9 Polymer blend with D and F 10th 13 10th Polymer blend with E and F 10th 22 11 Polymer blend with D and G. 15 25th PVA (88/5) 88% saponified polyvinyl alcohol (obtained from polyvinyl acetate), viscosity (4% in water, 20 ° C.) 5 mPa · s 32 > 90

Als Vergleich zu den erfindungsgemäßen Polymermischungen wurden solche mit den Einzelkomponenten A und B gegenübergestellt. Tabelle 4 zeigt die Ergebnisse der Bestimmung der Stabilität und Viskosität der erfindungsgemäßen Polymermischungen 8, 9 und 10. Die vergleichenden Mischungen wurden aus einer der Einzelkomponente A oder B, Polyvinylalkohol und Wasser sowie der Einzelkomponente F hergestellt.As a comparison to the polymer mixtures according to the invention, those with the individual components A and B were compared. Table 4 shows the results of the determination of the stability and viscosity of the polymer mixtures 8, 9 and 10 according to the invention. The comparative mixtures were prepared from one of the individual components A or B, polyvinyl alcohol and water and from the individual component F.

Die erfindungsgemäßen Polymermischungen 8 bis 10 sind gegenüber den Mischungen mit den Einzelkomponenten A und B mischungsstabil. Tabelle 4 Stabilität und Viskosität der erfindungsgemäßen Polymermischungen 8 bis 10 im Vergleich mit Mischungen aus Einzelkomponenten mit niedrigem Polyvinylalkoholanteil Verwendetes Methacrylat-Beispiel Acrylat/Copolymer PVA-Gehalt [%] Stabilität der Mischung Viskosität der 15%igen Flotte A 2 Trennung nach 4 Tagen 70/ 50 B 4 Trennung nach 7 Tagen 80/ 50 C 10 keine Trennung 120/110 D 19 keine Trennung 235/275 E 25 keine Trennung 215/225 The polymer mixtures 8 to 10 according to the invention are stable to the mixtures with the individual components A and B. Table 4 Stability and viscosity of the polymer mixtures 8 to 10 according to the invention in comparison with mixtures of individual components with a low polyvinyl alcohol content Methacrylate example used Acrylate / copolymer PVA content [%] Stability of the mixture Viscosity of the 15% liquor A 2nd Separation after 4 days 70/50 B 4th Separation after 7 days 80/50 C. 10th no separation 120/110 D 19th no separation 235/275 E 25th no separation 215/225

Claims (6)

  1. The use of copolymers which are obtainable by free radical emulsion or solution polymerization of
    A) from 50 to 95 % by weight of a C₁-C₈-alkyl acrylate and/or methacrylate,
    B) from 5 to 20 % by weight of an unsaturated carboxylic acid and/or anhydride,
    C) from 0 to 20 % by weight of further water-soluble comonomers, and
    D) from 0 to 10 % by weight of other comonomers
    in the presence of
    E) from 2 to 60 parts by weight of a polyvinyl alcohol per 100 parts by weight of the monomer mixture of A) to D)
    and which are completely or partially present as alkali metal, alkaline earth metal or ammonium salts, as size for stapel fiber and filament yarns.
  2. A use as claimed in claim 1, wherefor the copolymers are obtainable by free radical emulsion or solution polymerization of
    A) from 70 to 80 % by weight of a C₁-C₈-alkyl acrylate and/or methacrylate,
    B) from 5 to 20 % by weight of an unsaturated carboxylic acid and/or anhydride,
    C) from 0 to 20 % by weight of further water-soluble comonomers, and
    D) from 0 to 10 % by weight of other comonomers
    in the presence of
    E) from 10 to 40 parts by weight of a polyvinyl alcohol per 100 parts by weight of the monomer mixture of A) to D).
  3. A use as claimed in claim 1 or 2, wherefor at least 50% of the copolymers are present as sodium, calcium, magnesium, ammonium or C₁- to C₄-alkylammonium salt.
  4. A size comprising
    a) from 20 to 60 % of the partially or completely neutralized copolymer to be used as claimed in claim 1,
    b) from 10 to 40 % by weight of a polyvinyl alcohol,
    c) from 20 to 60 % by weight of a completely or partially neutralized, sulfo- and/or carboxylcontaining polyester which is formed from a nonaromatic C₂-C₆-diol and a mixture of an aromatic dicarboxylic acid and an aromatic tricarboxylic and/or sulfodicarboxylic acid and is water-soluble in salt form, and
    d) from 0 to 10 % by weight of customary additives.
  5. A size comprising
    a) from 40 to 60 % of a copolymer to be used as claimed in claim 3,
    b) from 10 to 25 % by weight of a polyvinyl alcohol,
    c) from 20 to 50 % by weight of a completely or partially neutralized, sulfo- and/or carboxylcontaining polyester which is formed from a nonaromatic C₂-C₆-diol and a mixture of an aromatic dicarboxylic acid and an aromatic tricarboxylic and/or sulfodicarboxylic acid and is water-soluble in salt form, and
    d) from 0 to 10 % by weight of customary additives.
  6. The use of the size of claim 4 or 5 for the processing of microfiber yarns, multifilament yarns and textured or flat filament yarns.
EP91104620A 1990-04-02 1991-03-23 Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use Expired - Lifetime EP0450437B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4010563 1990-04-02
DE4010563A DE4010563A1 (en) 1990-04-02 1990-04-02 COPOLYMERISATE BASED ON C (DOWN ARROW) 1 (DOWN ARROW) -C (DOWN ARROW) 8 (DOWN ARROW) ALKYL ACRYLATES AND / OR METHACRYLATES

Publications (3)

Publication Number Publication Date
EP0450437A2 EP0450437A2 (en) 1991-10-09
EP0450437A3 EP0450437A3 (en) 1992-04-08
EP0450437B1 true EP0450437B1 (en) 1995-06-07

Family

ID=6403582

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91104620A Expired - Lifetime EP0450437B1 (en) 1990-04-02 1991-03-23 Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use

Country Status (6)

Country Link
US (1) US5231145A (en)
EP (1) EP0450437B1 (en)
JP (1) JPH04224811A (en)
DE (2) DE4010563A1 (en)
ES (1) ES2073057T3 (en)
PT (1) PT97218B (en)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2220419A1 (en) * 1992-04-01 1996-11-14 Henkel Corporation Composition and process for treating metal
DE4213514A1 (en) * 1992-04-24 1993-10-28 Basf Ag Use of water-soluble or water-dispersible suspension polymers as textile fiber sizing agents
CA2110448A1 (en) * 1992-12-08 1994-06-09 Helen H.Y. Pak-Harvey Redispersible acrylic polymer powder for cementitious compositions
JP3416194B2 (en) * 1993-04-26 2003-06-16 株式会社ジーシー Separation material for denture base
DE4318033C2 (en) * 1993-05-29 1996-08-29 Hoechst Ag Copolymers containing carboxyl groups in aqueous dispersion form or redispersible powder form and their water-soluble salts, processes for their preparation and their use as thickeners in aqueous preparations
US5405653A (en) * 1994-02-28 1995-04-11 E. I. Du Pont De Nemours And Company Poly(vinyl alcohol)starch blends for textile sizes with improved ability to be desized
US5362515A (en) * 1994-02-28 1994-11-08 E. I. Du Pont De Nemours And Company Poly(vinyl alcohol)copolymer sizes having high capacity to be desized
US5436293A (en) * 1994-02-28 1995-07-25 E. I. Du Pont De Nemours And Company Poly(vinyl alcohol) polymer blend textile sizes with improved ability to be desized
DE4407842A1 (en) * 1994-03-09 1995-09-14 Huels Chemische Werke Ag Protective colloid-stabilized polyacrylate dispersions
GB9422093D0 (en) * 1994-11-02 1994-12-21 Zeneca Ltd Rheology modifier for solvent-based coatings
DE4447359C5 (en) * 1994-12-21 2009-01-02 ALTERFIL Nähfaden GmbH Bauschiges sewing thread
US5741871A (en) * 1996-06-14 1998-04-21 Air Products And Chemicals, Inc. Acrylic emulsions prepared in the presence of fully hydrolyzed poly (vinyl alcohol)
KR100448933B1 (en) * 1996-07-01 2004-11-26 가부시키가이샤 구라레 Fiber liner
US5753036A (en) * 1997-04-21 1998-05-19 Air Products And Chemicals, Inc. Poly(vinyl alcohol) stabilized acrylic polymer modified hydraulic cement systems
JP2002529603A (en) * 1998-07-01 2002-09-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Poly (vinyl alcohol) copolymer ionomer, its preparation, and its use in fabric size
US6114417A (en) * 1998-10-16 2000-09-05 Cytec Technology Corp. Paper sizing agents and methods
FR2785629B1 (en) * 1998-11-10 2000-12-22 Coatex Sa POLYMERIC COMPOSITION FOR WATER RETENTION AND ACTIVATOR OF OPTICAL BRIGHTENERS, COATING SAUCES FOR PAPER, AND SHEETS OF COATED PAPER THUS OBTAINED
DE19857897A1 (en) * 1998-12-15 2000-06-21 Basf Ag Process for the preparation of aqueous polymer dispersions
DE19960863A1 (en) * 1999-12-17 2001-06-28 Basf Ag Polymers stabilized with polyvinyl alcohol to enhance the optimal brightening of coating materials
ITSV20020051A1 (en) * 2002-10-11 2004-04-12 Allaix Roberto C O Ferrania S P A Uff Brevetti SUMMARY OF A COPOLYMER IN THE FORM OF PARTICLES CONTAINING HYDROFILE FUNCTIONALITY.
KR100659455B1 (en) * 2004-11-09 2006-12-19 주식회사 엘지화학 Additive for vinyl chloride resin and vinyl chloride resin composition having thereof
JP4888853B2 (en) 2009-11-12 2012-02-29 学校法人慶應義塾 Method for improving visibility of liquid crystal display device, and liquid crystal display device using the same
EP2558638A1 (en) * 2010-04-15 2013-02-20 Basf Se Treatment of textile and formulations suitable therefor
MX342229B (en) 2010-06-21 2016-09-21 Basf Se Sound damping compositions and methods for application and use.
KR101699497B1 (en) 2010-06-22 2017-01-24 도요보 가부시키가이샤 Liquid crystal display device, polarizing plate and polarizer protective film
CN106094091B (en) 2011-05-18 2019-03-15 东洋纺株式会社 Polarizer and polaroid protective film
US10175494B2 (en) 2011-05-18 2019-01-08 Toyobo Co., Ltd. Polarizing plate suitable for liquid crystal display device capable of displaying three-dimensional images, and liquid crystal display device
CN102505485B (en) * 2011-10-20 2013-08-21 天津工业大学 Hair slip prevention finishing agent and finishing method for rabbit hair fabric
CN104520738B (en) * 2012-08-07 2017-02-01 东洋纺株式会社 Polyester film for polarizer protection, polarizing plate and liquid crystal display device

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3546008A (en) * 1968-01-03 1970-12-08 Eastman Kodak Co Sizing compositions and fibrous articles sized therewith
GB1278813A (en) * 1969-08-27 1972-06-21 High Polymer Chemical Ind Ltd Method of preparation of acrylic polymer latices
JPS5039685B1 (en) * 1970-07-03 1975-12-18
DE2256154C3 (en) * 1972-11-16 1984-10-04 Basf Ag, 6700 Ludwigshafen Process for the preparation of aqueous dispersions of polymers of monoolefinically unsaturated carboxylic acid esters
JPS515871B2 (en) * 1973-01-19 1976-02-23 Nippon Synthetic Chem Ind
US3909477A (en) * 1973-06-27 1975-09-30 Dow Chemical Co Warp-sizing compositions and yarns sized therewith
DE2714897C3 (en) * 1977-04-02 1981-12-03 Basf Ag, 6700 Ludwigshafen Use of water-soluble alkaline earth salts of polymers of acrylic acid or methacrylic acid as sizing agents
DE2842719A1 (en) * 1978-09-30 1980-04-10 Basf Ag METHOD FOR PRODUCING AQUEOUS POLYACRYLATE DISPERSIONS WITH IMPROVED FLOW BEHAVIOR
DE3167114D1 (en) * 1980-11-24 1984-12-13 Akzo Nv A sized multifilament yarn of an aromatic polyamide, a yarn package, a woven fabric and a process for making said yarn
DE3111602A1 (en) * 1981-03-24 1982-10-07 Wacker-Chemie GmbH, 8000 München COPOLYMERISATE OF INCREASED WATER RESISTANCE, METHOD FOR THEIR PRODUCTION AND THEIR USE
US4470505A (en) * 1983-01-26 1984-09-11 Paul Korwin Method and apparatus for storing, mixing and delivering dental amalgam
EP0144155B1 (en) * 1983-11-07 1989-03-15 Showa Denko Kabushiki Kaisha Agent for forming surface-protecting layer on coated paper
US4670505A (en) * 1985-08-23 1987-06-02 Hercules Incorporated Polyacrylate dispersions
JPS62288076A (en) * 1986-06-06 1987-12-14 Honshu Paper Co Ltd Sheet for ink jet recording

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 76-06468X & JP-B-50 039 685 *

Also Published As

Publication number Publication date
PT97218A (en) 1992-01-31
DE59105640D1 (en) 1995-07-13
PT97218B (en) 1998-07-31
US5231145A (en) 1993-07-27
ES2073057T3 (en) 1995-08-01
EP0450437A3 (en) 1992-04-08
EP0450437A2 (en) 1991-10-09
DE4010563A1 (en) 1991-10-10
JPH04224811A (en) 1992-08-14

Similar Documents

Publication Publication Date Title
EP0450437B1 (en) Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use
EP0019169B1 (en) Use of an aqueous dispersion of an emulsion copolymer that contains amide groups for bonding nonwovens
EP0735065B1 (en) Amphoteric polymer dispersion, process for preparation and its use
DE69410014T2 (en) Emulsion interpolymer composition of vinylidene chloride
DE1495645C3 (en) Process for the production of stable, aqueous emulsions or dispersions of ethylene copolymers
EP0376096A2 (en) Aqueous dispersion of a multiphase plastic material and its use in coating compositions
DE2459160C3 (en) Process for the preparation of aqueous dispersions of copolymers of non-tertiary acrylic acid esters
DE68922755T2 (en) Rapid crosslinking binder for cellulose.
DE2149282A1 (en) PAPER COATINGS
DE2161408A1 (en) Latex compound and process for its manufacture
DE2513162A1 (en) MIXTURE OF SURFACE-ACTIVE SUBSTANCES
DE69725779T2 (en) Sizing paper with latex dispersions from copolymers of hydrophobic monomers and low molecular weight styrene / maleic anhydride polymers
DE3750209T2 (en) Nonwoven fabric with an acrylic interpolymer binder and process for making the same.
DE60104334T2 (en) FORMALDEHYDE-FREE NETWORKED CORE-BOWL-LATEX FOR TEXTILES
DE2536810A1 (en) METHOD FOR TREATMENT OF FABRICS
DE2454397A1 (en) Cationic aqueous copolymer dispersions - by copolymerising unsaturated monomers in presence of aqueous solution of nitrogen-containing copolymer
DE3750210T2 (en) Elastic latex film, molded articles from this film and method of making this film.
DE2538183A1 (en) PROCESS FOR MAKING SALT-RESISTANT LATICES
EP0400410B1 (en) Process for sizing paper
DE2162285A1 (en) Poly (vinyl acetate-dialkyl maleate-acrylic acid) textile glue
EP0320609B1 (en) Anionic paper surface sizing agent
DE2136312A1 (en) Vinyl acetate polymer and method for making the same
DE854851C (en) Process for the production of interpolymers
WO2007057344A1 (en) Temporary binding agent
EP0532961A1 (en) Graft copolymers from polyesters containing sulfonic acid groups as trunk polymers, process for their preparation and their use

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE ES FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE ES FR GB IT NL

17P Request for examination filed

Effective date: 19920306

17Q First examination report despatched

Effective date: 19931207

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL

REF Corresponds to:

Ref document number: 59105640

Country of ref document: DE

Date of ref document: 19950713

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950623

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2073057

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960223

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960229

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960313

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960314

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960315

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960326

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970312

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19970324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970331

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19970331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19971001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971128

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19991102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050323